Automatic dishwashing compositions containing rinse agent

ABSTRACT

A cleaning composition particularly adapted for washing dishes, glasses and silverware in mechanical devices such as automatic dishwashers and capable of reducing spotting and filming thereof, and essentially free of halide bleaching compounds, containing as the essential ingredients about 1-20% sucrose, 0.5-10% of an enzyme and 40-95% of at least one water-soluble organic and/or inorganic builder salt.

KR li /821,118

United States Patent [191 Finck ]*June 28, 1974 [5 AUTOMATIC DISHWASHING3,519,379 7/1970 COMPOSITIONS CONTAINING RINSE 3,549,539 12/1970 AGENT3,627,686 l2/l97l 3,637,339 l/l972 Inventor: Patricia A. Finck, JerseyCity, NJ. 5,5 4/ 2 [73] Assignee: Colgate-Palmolive Company, New

York, NY. Primary Examzner-Mayer Wemblatt Notlcei The P of the term ofthls Attorney, Agent, or Firm-Herbert S. Sylvester; Mur- 099 1989, rayM. Grill; Norman Blumenkopf [22] Filed: Dec. 3, 1971 [21] Appl. No.:204,752 57 ABSTRACT Related US. Application Data 1 [63] g 22; April Acleaning composition particularly adapted for washing dishes, glassesand silverware in mechanical de- 52 US. Cl 252/99, 8/108 252/ such asautomatic dishwashers and capable 252/ reducing spotting and filmingthereof, and essentially [5]] km CL Clld 7/16, C1 M 7/14, C] m 7/08 freeof halide bleaching compounds, containing as the [58] Field of Search252/99 95, 8/108 essential ingredients about 1-20% sucrose, O.5-l0% ofan enzyme and 40-95% of at least one water-soluble [56] References Citedorganic and/or inorganic builder salt.

UNITED STATES PATENTS 2/1966 Tuvell 252/l35 16 Claims, No DrawingsAUTOMATIC DISHWASHING COMPOSITIONS CONTAINING RINSE AGENT The presentinvention is a continuation-in-part of copending application Ser. No.133,338 now US. Pat. No. 3,701,735 and relates in general to cleaningcompositions and in particular to the provision of cleaning compositionsbeneficially adapted for use in connection with the spot and film-freecleaning of tableware.

Many of the cleaning compositions heretofore recommended for use inconnection with the cleaning of tableware have been subject to one ormore significant disadvantages. Perhaps the paramount difficultyinvolved relates to the tendency of such compositions to leaveundesirable spots and streaks on the washed tableware. As will berecognized, aesthetic considerations rather than purely functionalcriteria are often of overriding importance as regards the suitabilityof a given cleaning composition and especially when contemplated for usein connection with the cleaning of tableware. Without intending to bebound by any theory, it has nevertheless been hypothesized inexplanation of the spotting and filming phenomenon that the presence ofpolyvalent metals such as calcium, magnesium, etc. normally found in tapwater, precipitate out in the presence of the strongly alkaline cleaningsolutions and deposit on the tableware. In addition, the presence ofhigh food soil concentrations may cause excessive foaming, due tosaponification of fatty food soils in the alkaline cleaning solutions,which interferes with the mechanical cleaning action by reducing thepressure at which the washing fluid is impelled against the tableware inthe machine.

In an effort to overcome or otherwise ameliorate the foregoing andrelated difficulties, considerable research activity has been necessaryin the development of cleaning compositions specifically andadvantageously adapted to minimize the spotting and filming problem andyet capable of providing the requisite measure of cleaning activity.Thus, much of the methodology heretofore promulgated involves as anessential expedient the use of one or more additives which purportedlyfunction as rinse additives in the final rinse as a separate anddistinct operation in the mechanical washing of tableware. In thisregard, a final and separate rinse has been recommended by the prior artafter a clear water. rinse (to rid the solution of the alkali found inthe wash stage), which contain a water-soluble starch degradationproduct and/or a sugar; or an ester of a sugar and a fatty acid; or alow foaming organic polyethenoxy non-ionic surfactant and apolyoxyalkylene glycol mixture; etc. Although a final rinse with acomposition has proved somewhat effective in overcoming the spotting andfilming problem, the necessity of utilizing a separate rinse additive iscumbersome, inconvenient and an added expense in the use of automaticmachine dishwashers.

Accordingly, it has now been discovered that the inclusion of bothsucrose and an enzyme directly in the detergent formulation surprisinglyeffects a reduction in the spotting and filming of tableware withoutadversely affecting its cleaning efficacy, and completely eliminates theseparate rinsing step heretofore found necessary. In addition, the totalelimination of the halide bleach from the dishwasher detergent hasrendered the product less corrosive and consequently more effective inflim and spot removing of metallic utensils.

While the proportion of sucrose in a detergent formulation may bevaried, a desirable range is from about 1% to 20% by weight of the totalformulation, a preferred range being from approximately 2% by weight toapproximately 10% by weight of the total formulation. The enzyme contentmay vary between 0.5 to 10% by weight, depending on the specific enzymeor combination of enzymes utilized.

Thus, a primary object of the present invention resides in the provisionof cleaning compositions capable of providing essentially spot-freetableware.

Another object of the present invention resides in the provision ofcleaning compositions capable of providing superior cleaning activity,in the absence of a halide bleaching agent.

Still another object of the present invention resides in the provisionof cleaning compositions capable of providing essentially film-freetableware.

Other objects and advantages of the present invention will become moreapparent hereinafter as the description proceeds.

In accordance with the present invention, a watersoluble alkalinedetergentcomposition for automatic dishwashing essentially free ofhalide bleaching compounds, comprises about 40-95% by weight of at leastone water soluble organic and/or inorganic builder salt; about l-20% byweight sucrose, and about 0.5-10% by weight of at least one enzyme.

It is an essential feature of this invention that the composition befree of halide bleach, i.e., compounds capable of releasing hypohaliteions such as hypochlorite chlorine and/or hypobromite bromine on contactwith aqueous media. It has been found that said halide bleaches areincompatible with and deactivate the enzyme constituents. However,oxygen bleach such as peroxygen compounds, more specifically sodiumperborate and persulfate (oxone), are compatible with the enzymes andenhance stain removal activity especially coffee and tea stains.Accordingly, oxygen bleach may be used as an additional constituent,although not an essential ingredient of instant composition in amountsup to 20% by weight of the total composition, and preferably in amountsof about 5-10% by weight thereof.

The sucrose contemplated for use in the practice of the presentinvention and capable of substantially reducing both spotting andfilming of tableware is watersoluble, and may be either fine orgranulated. Sucrose is a disaccharide composed of D-glucose and D-fructose, having the chemical formula C I-I 0 and also known assaccharose and saccharobiose. Commercially, sucrose is known as sugar,and is produced from cane sugar (ordinary table sugar), beet sugar,maple sugar, and sorghum sugar. The type and amount of sugar utilized isdependent on availability, cost and compatibility with the otheringredients of the detergent composition. However, the granulated fonnof sugar has been found preferable because of the ease with which it canbe blended with the other ingredients. It has been found that amounts aslow as 1% sucrose by weight are effective in obtaining superiorinhibition of spotting and filming of tableware washed in a mechanicaldishwasher, although the preferred range is 2 to 10% by weight of thetotal detergent composition.

The water soluble builder salts utilized in the instant detergentcomposition comprise one or more inorganic and/or or organic basic andneutral water soluble salts. The builder salts are employed in amountsranging up to about 95%, i.e. 4095% by weight with a range of from about60% to about 90% by weight of the composition being preferred. Suitableinorganic builders include without necessary limitation, trisodiumphosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodiumtripolyphosphate hexahydrate, sodium monobasic phosphate, sodium dibasicphosphate, sodium hexameta phosphate, sodium silcates, SiO Na O of U1 to3.2/1 (sodium metasilicate), sodium carbonate, sodium sulfate, borax,etc. Suitable organic builders include salts of organic acids and, inparticular, the water soluble salts of aminopolycarboxylic acids andhydroxycarboxylic acids. The alkali metal salts such as sodium,potassium and lithium; ammonium and substituted ammonium salts such asmethylammonium, diethanolammonium and triethanolammonium; and aminesalts such as mono, diand triethanolamine, methylamine, octylamino,diethylenetriamine, triethylenetetramine and ethylenediamino areefficacious. The acid portion of the salt can be derived from acids suchas nitrilodiacetic; N-(Z-hydroxyethyl) nitrilodiacetic acid,nitrilotriacetic acid (NTA), ethylenediamine tetracetic acid, (EDTA);N-(2-hydrooxyethyl) ethylene 'diamine triacetic acid; 2-hydroxyethyliminodiacetic acid; 1, 2-diaminocyclohexanediacetic acid;diethylenetriamine penta-acetic acid, citric acid and the like. Thebuilder salt is preferably employed in amounts sufficient to yield a pHin water of from 9.5 to 12 preferably from to 1 l in order to obtainoptimum detergency performance.

The cleaning compositions described herein are further provided with oneor more enzymes which may in general be defined as encompassingcompounds capable of degrading soil materials such as starch,carbohydrates and proteins.

In the preferred form of the invention the enzyme comprises aproteolytic enzyme which is active upon protein matter and catalyzesdigestion or degradation 4 of such matter when present on tableware in ahydrolysis reaction. Generally, the enzymes are effective in a pH rangeof about 4-1 2, and are effective even at moderately high usetemperatures. They are also effective at ambient temperature andtemperatures of about 10 C. Particular examples of proteolytic enzymeswhich may be used in the instant invention include pepsin, trypsin,chymotrypsin, papain, bromeline, colleginase, keratinase, carboxylase,amino peptidase, elastase, subtilisin and aspergillopeptidase A and B.Preferred enzymes are subtilisin enzymes manufactured and cultured fromspecial strains of spore forming bacteria, particularly Bacillussubtilis.

Proteolytic enzymes such as Alcalase (1.5 and 4.0 Anson Units),Maxatase, 300,000, 330,000 and 500,000, Protease APlOX, Protease ATP40,Protease ATO 120, Protease L-252, Protease L-423, Protease ATP 360,Alkaline Protease No. 1, Proteinase GV, Protease 2200 C, Protease A 300,Protein AS 7, Enzyme P and Bioprase AL 15 are among those enzymesderived from strains of spore forming Bacillus, such as Bacillussubtillis.

Different proteolytic enzymes have different degrees of effectiveness inaiding in the removal of stains from tableware. Particularly preferredas stain removing enzymes are subtilisin enzymes.

Metalloprotease which contain divalent ions such as calcium, magnesiumor zinc bound to their protein chains are also of interest.

The enzyme preparations are generally extremely fine powders. In atypical powdered enzyme preparation the particle diameter generallyranges from 0.01 mm to 0.15 mm, eg about 0.1 mm, and as much as of thematerial may pass through a 100 mesh (US. Standard) sieve. On the otherhand the spray dried granules are usually of very much larger particlesize, with the major portion of the granules being from about 0.2 mm to2.0 mm in diameter.

The commercial enzyme preparations are generally diluted with inorganicsalts, e.g., alkali metal and alkaline earth metal salts. Typically theenzyme comprises from 1% to by weight of the enzyme preparation. Forexample, a typical Alcalase enzyme material analyzes (by weight) 6.5%enzyme, 4% water, 70% sodium chloride, 15.5% sodium sulfate, 3.5%calcium sulfate, and 0.5% organic impurities. Chemically they aretypically stable in the pH range of 5 to 12. Generally, they areeffective against various types of soil in an aqueous medium having atemperature of about 20C to about 80C. Naturally, different proteolyticenzymes have different degrees of effectiveness in aiding in the removalof specific stains from tableware.

Instead of, or in addition to, the proteolytic enzyme, an amylase may bepresent such as a bacterial amylase of the alpha type (e.g. obtained byfermentation of B. subtilis). One very suitable enzyme mixture containsboth a bacterial amylase of the alpha type and an alkaline protease,preferably in proportions to supply about 10,000 to 400,000 Novoalpha-amylase units per Anson unit of said alkaline protease.

On a solids basis, i.e., a water-free basis, the enzyme preparationcontent of the granules or beads can be varied widely and generally willbe in the range of 2% to 50% by weight of enzyme preparation or 0.1% to5% by weight of active enzyme. When the particulate enzyme preparationhas an alkaline protease content of 1.5 Anson units per gram, this rangeof course represents some 3 to 75 Anson units per grams of granules orbeads. The invention finds its greatest utility, however, for themanufacture of granules or beads which are relatively high in enzymepreparation content, containing at least 8% by weight of the enzymepreparation(corresponding to say at least 12 Anson units per 100 gramsof the granules) and preferably at least 10% by weight. In the finalwashing product, made for example by blending the enzyme containinggranules or beads with other granular material (such as spray-driedhollow beads or spongeous low density granules), the content of powderedenzyme preparation is much lower, e.g., in the range of about 0.1% to5.0

Water soluble organic detergents, i.e. surface active components may beemployed, such materials being well known in the prior art, the termdetergent comprehending species of the anionic, cationic, amphoteric andzwitterionic types. In formulating an automatic dishwasher product, itis preferred to utilize a low foaming detergent such as the non-ionics.

Nonionic surface active agents include those surface active or detergentcompounds which contain an organic hydrophobic group and a hydrophilicgroup which is a reaction product of a solubilizing group such ascarboxylate, hydroxyl, amido or amino with ethylene oxide or with thepolyhydration product thereof, polyethylene glycol.

As examples of nonionic surface active agents which may be used theremay be noted the condensation products of alkyl phenols with ethyleneoxide, e.g., the reaction product of isooctyl phenol with about 6 to 30ethylene oxide units; condensation products of alkyl thiophenols with 10to ethylene oxide units; condensation products of higher fatty alcoholsof monoesters of hexahydric alcohols and inner ethers thereof such assorbitan monolaurate, sorbitol mon-oleate and mannitan monopalmitate,and the condensation products of polypropylene glycol with ethyleneoxide.

Further suitable detergents are polyoxyalkene esters of organic acids,such as the higher fatty acids, resin acids, tall oil, or acids from theoxidation of petroleum, and the like. The polyglycol esters will usuallycontain from about 8 to about 30 moles of ethylene oxide or itsequivalent and about 8 to 22 carbon atoms in the acyl group. Suitableproducts are refined tall oil condensed with 16 or 20 ethylene oxidegroups, or similar polyglycol esters of lauric, stearic, oleic and likeacids.

Additional suitable non-ionic detergents are the polyalkylene oxidecondensates with higher fatty acid amides, such as the higher fatty acidprimary amides and higher fatty acid monand di-ethanol-amides. Suitableagents are coconut fatty acid amide condensed with about 10 to 30 molesof ethylene oxide. The fatty acyl group will similarly have about 8 to22 carbon atoms, usually about 10 to 18 carbon atoms in each product.The corresponding sulphonamides may also be used if desired.

Other suitable polyether non-ionic detergents are the polyalkylene oxideethers of higher aliphatic alcohols. Suitable alcohols are those havinga hydrophobic character, and preferably 8 to 22 carbon atoms. Examplesthereof are iso-octyl,nonyl, decyl, dodecyl, tridecyl, tetradecyl,hexadecyl, octadecyl and oleyl alcohols which may be condensed with anappropriate amount of ethylene oxide, such as at least about 6, andpreferably about 10-30 moles. A typical product is tridecyl alcohol,produced by the 0x0 process, condensed with about l2, 15 or 20 moles ofethylene oxide. The corresponding higher alkyl mercaptans orthioalcohols condensed with ethylene oxide are also suitable for use incompositions of the present invention.

Examples of other suitable wetting agents include low foaming anionicmaterials such as dodecyl hydrogen phosphate, methyl naphthalenesulfonate, sodium 2-acetamido-hexadecane-l-sulfonate, and mixturesthereof. Mixtures of the foregoing wetting agents may also be employed,and if desired, foam-reducing additive may be added as appropriate tominimize undesirable foaming tendencies of these wetting agents underconditions of use.

The detergent material is employed in concentrations ranging from about0.5% to about 5% by weight of total composition with a range of 1% to 3%being particularly preferred.

Thus, a relatively minor amount of nonionic type detergent, that is,about 24% is especially beneficial inasmuch as it acts as a foamdepressant as well as a detersive agent in an automatic dishwashingsolution.

Minor amounts of other additives which do not interfere with thecleaning properties of instant composition may be added such aspigments, dyes, perfume, fillers, extenders, suds builders, sudsdepressors, antiredeposition agents, polyelectrolytes which function assoil suspending and/or peptizing agents including polycarboxylates,polyarninomethyl phosphonate, maleic anhydride-acrylic acid polymer,starch degradation products, polymethyl vinyl ether/maleic acid, and thelike, overglaze protectors including aluminum acetate, aluminum formate,sodium and aluminum phosphate, alkali aluminate, zincate, berylliate,perfumes, boric oxide, boric anhydride, etc. In some instances it may becommercially feasible to add said ingredients to render them moreattractive to the consumer.

The following examples are given for purposes of illustration only andare not to be considered as necessarily constituting a limitation on thepresent invention. All parts and percentages given are by weight unlessotherwise indicated. The compositions are prepared usually bydry-blending the ingredients to form a dry, particulate product such asa free-flowing granular composition or powder. For purposes ofascertaining the capacity of the various compositions exemplified toreduce spotting and filming of tableware, the method of the ChemicalSpecialties Manufacturers Association (CSMA) is employed, such methodbeing described in detail in Soap and Chemical Specialities, 33, (9),60, 1957. This method is designed for testing formulations for use indishwashers to show spotting and film buildup on glass tumblers and/orphotographic plates in the presence of a standard soil comprisingmargarine and 20% starlac by equally loading a dishwasher with fiveglass tumblers and five photographic plates on the upper rack and sixlarge dinner plates plus smaller plates on the bottom rack; adding thestandard soil to the dishwasher; placing 30 grams of detergent in eachcup for a 0.3% concentration; introducing tap water at F and running themachine through a complete cycle. The contents are cooled to 75 F andvisually rated in the presence of good light in accordance with thefollowing scale:

1. glass spotless or film-free 2. spots at random or barely perceptiblefilm 3. one-fourth of glass covered with spots or apparent 4. one-halfglass covered with spots or moderate film 5. glass completely coveredwith spots or heavy film Utensils of stainless steel, silverware,copperware and aluminum ware may also be included for testing purposes.

EXAMPLE I Ingredients Sodium tripolyphosphate hexahydrate Sodiummetasilicate, anhydrous Sodium sulfate, anhydrous Non-ionic detergentColor Water Perfume Alcalase Sucrose 7 The non-ionic detergent is theproduct obtained by the condensation of about three moles of propyleneoxide with the condensation product of one mol of a mixture ofessentially straight chain, primary fatty alcohols in the C -C rangewith about .6 moles of ethylene oxide.

EXAMPLE 2 Ingredient Na tripo1yphosphate6H,O 40.0 Na metasilicate 15.0Na sulfate, anhydrous 10.0 Nonionic of Example 1 2.0 H 0.28 Perfume 0.02Sucrose 6.0 Na citrate 24.6 Alcalase 2.0 Color 0.1

Results of evaluations of the tableware are tabulated below as anaverage of four washes. (Rating scale: l no spotting or filming to heavyspotting or filming). The bleach no sugar nor enzyme formula is acontrol containing 2% potassium dichlorocyanurate and equivalent to Ajaxautomatic dishwasher detergent.

No Bleach,

Formula Bleach No Sugar Sugar & Enzyme or enzyme (Ex. 2) spottingfilming Glass l 1.7 l 2 l Tumblers (2) 1.7 1.7 2 l (3) 2 2.2 2.5 1.2 (4)1.5 1.7 2.2 l (5) 2 2.2 2.2 1.2 Glass (1) 1.7 2.5 2.7 1 Photo (2) 1.72.5 2.2 l Plates (3) 2 2.7 2.5 l (4) 1.7 2.7 2.5 l (5) 2 2.7 3 1Stainless slight spotting OK Silverware filming & spotting slightspotting As the above data makes manifestly clear, instant formulationprovides a substantial improvement in the elimination of filming oftableware inclusive of stainless steel, silverware, glass tumblers andplates. The control composition without the sugar and enzyme exhibitedfilming of silverware, stainless steel, plates and glassware.

EXAMPLE 3 Ingredients Sodium tripolyphosphate hexahydrate Sodiummetasilicate. anhydrous Sodium sulfate, anhydrous Non-ionic detergent ofEx. 1

Alcalase Sucrose Sodium acid aluminum phosphate (overglaze protector) Inaddition to yielding substantially spot and film free tableware, thiscomposition exhibited superior overglaze protection when the sucrose andenzyme are present, i.e., a synergistic efiect in overglaze protectionof fine china is produced by the combination of overglaze protectingagent, sucrose and enzyme.

EXAMPLE 4 Example 3 is repeated except that the sodium acid aluminumphosphate is omitted and 6% boric anhydride added and the sodium sulfatereduced to 2.6%. The results obtained are similar to those of Example 3.

EXAMPLE 5 Example 3 is repeated except that 6% boric anhydude is addedand the sodium sulfate is omitted and the phosphate content reduced to61.1%.

EXAMPLE 6 Example 3 is repeated, but 3% boric anhydride is added and thesodium sulfate is reduced to 2.6%

EXAMPLE 7 Ingredients Sodium citrate-2H O Nonionic of Ex. 1

Alcalase Sucrose Sodium metasilicate, anhydrous, granular Sodiumcarbonate, light granular Sodium sulfate, anhydrous Boric Acid BoricOxide *Polyamino methyl phosphonate Perfume obtained from MonsantoEXAMPLE 8 Ingredients Sodium nitrilotriacetate Sodiumethylene-diaminetetracetate Polyamino methyl phosphonate AlcalaseNonionic of Ex. 1

Sucrose Sodium acid aluminum phosphate Soda Ash Sodium sulfate,anhydrous -Continued Ingredient H 0.28 Perfume 0.02 Sucrose 6.0 Nacitrate 24.6 Alcolase 2.0 Color 0. l

EXAMPLE 1 l Example 10 is repeated but the 5% sodium perborate isreplaced by 8% sodium persulfate and the sodium sulfate content isreduced to 2%.

The above formulations yield essentially spot and film free tableware,irregardless of the type of builder salt or salts present; said superiorresults being a function of the combination of the enzyme and sucrosecomponents in the presence of the highly alkaline medium and in theabsence of halide bleach. Variations in the amount of sucrose, in theabove formulae such as 2% and 9% sucrose, etc., also yield highlysatisfactory results. Similarly the enzyme content may be increased to5% and 9% and yield satisfactory results.

When the foregoing procedure is repeated but the sucrose and enzyme areomitted, undesirable spotting and filming is clearly evident. When theamount of sucrose and/or enzyme is increased substantially, such as toabout 70% with a corresponding decrease in the amount of builder salts,then the level of spotting and filming of tableware becomesunacceptable, with greater spotting and filming in waters of increasinghardness.

In addition, the exemplified procedure make unavoidably clear that thecompositions provided in accordance with the present invention arecapable of superior cleaning activity, i.e., displaying an outstandingcapacity to readily remove food deposits from a wide variety of glazeddishware and aluminum ware, without adversely affecting said glazedsurfaces.

Effective industrial bottle cleaning compositions may be provided inaccordance with the present invention by merely admixing with causticalkali whereby to provide a highly alkaline composition preferablyhaving a pH of about 12. Such compositions may be readily formulated inaccordance with the parameters hereinbefore described.

Results similar to those described in the foregoing examples areobtained when the procedures delineated therein are repeated butemploying in lieu of the specific non-ionic detergent identified avariety of materials selected from low-foaming nonionic, anionic,cationic, amphoteric and zwitterionic types. Moreover, nothing criticalresides in the selection of the enzyme and accordingly, any of thematerials hereinbefore recommended for such purposes may be readilyemployed to advantage. Similarly, any water soluble salt or combinationof salts can advantageously be used inclusive of the organic and/ororganic salts.

While the detergent composition of the present invention finds mostefficacious utilization in connection with the washing of the dishes andthe like in automatic dishwashers, naturally, the detergent may beutilized in other fashions as desired. Usually, however, the best modeof use will be in connection with automatic dishwashers which have theability of dispensing the detergent of the present invention in one ormore separate wash cycles. Accordingly, the detergent compositions ofthe present invention is added to the two receptacles, if such arepresent, in an automatic dishwasher. When the dishwasher is set intooperation, after the dishes have been suitably positioned therein, theautomatic devices of the dishwasher permit the addition of sufficientwater to produce a concentration of the detergent composition ofapproximately 0.15 to 0.5% by weight. The operation of the dishwasherresults in treating, that is, washing of the dishes with the aqueoussolution of the detergent composition. Usually, the sequence ofoperation in utilizing an automatic dishwasher results in one or morerinsing steps following the one or more washing cycles. In utilizing thedetergent composition of the present invention it will be noted that thetableware is substantially spotand filmfree without resorting to aseparate and distinct final rinse with rinsing aids. In addition, thesedetergent compositions are substantially non-corrosive to the overglazeon china and to aluminum ware.

It will be apparent that many changes and modifications of the severalfeatures described herein may be made without departing from the spiritand scope of the invention. It is therefore apparent that the foregoingdescription is by way of illustration of the invention rather thanlimitation of the invention.

What is claimed:

1. A water-soluble alkaline dishwasher detergent composition capable ofsubstantially reducing the spotting and filming of tableware andessentially free of halide bleaching compounds consisting essentially ofabout 40-95% by weight of at least one water-soluble netural to alkalineorganic and/or inorganic builder salt; about l-20% by weight of sucrose;and 0.5 to 10% by weight of enzyme capable of catalyzing digestion ordegradation of protein matter.

2. A composition according to claim 1 including from about 0.5 to 5% oforganic water-soluble nonionic, anionic, cationic, amphoteric orzwitterionic detergent.

3. A composition according to claim 1 wherein said enzyme is proteolyticenzyme or an amylase.

4. A composition according to claim 1 including water-soluble overglazeprotector capable of inhibiting attack on the overglaze of fine chinaand dishware.

5. A composition in accordance with claim 1, which also includes up to20% by weight of peroxygen bleach compound compatible with said enzyme.

6. A composition according to claim 1 wherein said enzyme is Alcalase.

7. A composition according to claim 1, wherein said builder is a mixtureof sodium tripolyphosphate hexa hydrate and sodium metasilicate.

8. A composition in accordance with claim 1, wherein the builder salt issodium citrate.

9. A composition according to claim 2 wherein said detergent is lowfoaming nonionic material and constitutes from 1.3% by weight ofcomposition.

10. A composition according to claim 2 wherein said detergent is theproduct obtained by the condensation of about 3 moles of propylene oxidewith the condensation product of one mole of a mixture of essentiallystraight chain, primary C C fatty alcohols with 0.6 mole ethylene oxide.

11. A composition according to claim 3 wherein said proteolytic enzymeis selected from the group consisting of pepsin, trypsin, chymotrypsin,papain, bromeline, colleginase, keratinase, carboxylase, amino pepti- 11 dase, elastase, subtilisin and aspergillopeptidase A and B.

12. A composition according to claim 4 wherein said overglaze protectoris selected from the group consisting of sodium acid phosphate, boricacid, boron anhydride and mixtures thereof.

13. A composition according to claim 9 wherein said nonionic detergentis selected from the group consisting of condensation products of alkylphenols with from about 6 to 30 moles of ethylene oxide, condensationproducts of alkyl thiophenols with 10 to moles of ethylene oxide,condensation products of higher fatty alcohols of monoesters ofhexahydricalchols and inner ethers thereof, the condensation products ofpolypropylene glycol with ethylene oxide and the concomposition definedin claim 4.

2. A composition according to claim 1 including from about 0.5 to 5% oforganic water-soluble nonionic, anionic, cationic, amphoteric orzwitterionic detergent.
 3. A composition according to claim 1 whereinsaid enzyme is proteolytic enzyme or an amylase.
 4. A compositionaccording to claim 1 including water-soluble overglaze protector capableof inhibiting attack on the overglaze of fine china and dishware.
 5. Acomposition in accordance with claim 1, which also iNcludes up to 20% byweight of peroxygen bleach compound compatible with said enzyme.
 6. Acomposition according to claim 1 wherein said enzyme is Alcalase.
 7. Acomposition according to claim 1, wherein said builder is a mixture ofsodium tripolyphosphate hexahydrate and sodium metasilicate.
 8. Acomposition in accordance with claim 1, wherein the builder salt issodium citrate.
 9. A composition according to claim 2 wherein saiddetergent is low foaming nonionic material and constitutes from 1.3% byweight of composition.
 10. A composition according to claim 2 whereinsaid detergent is the product obtained by the condensation of about 3moles of propylene oxide with the condensation product of one mole of amixture of essentially straight chain, primary C10-C16 fatty alcoholswith 0.6 mole ethylene oxide.
 11. A composition according to claim 3wherein said proteolytic enzyme is selected from the group consisting ofpepsin, trypsin, chymotrypsin, papain, bromeline, colleginase,keratinase, carboxylase, amino peptidase, elastase, subtilisin andaspergillopeptidase A and B.
 12. A composition according to claim 4wherein said overglaze protector is selected from the group consistingof sodium acid phosphate, boric acid, boron anhydride and mixturesthereof.
 13. A composition according to claim 9 wherein said nonionicdetergent is selected from the group consisting of condensation productsof alkyl phenols with from about 6 to 30 moles of ethylene oxide,condensation products of alkyl thiophenols with 10 to 15 moles ofethylene oxide, condensation products of higher fatty alcohols ofmonoesters of hexahydricalchols and inner ethers thereof, thecondensation products of polypropylene glycol with ethylene oxide andthe condensates of higher fatty acid amides or sulphonamides with about10 to 30 moles ethylene oxide.
 14. A method for treating glasses, dishesand like tableware to remove foreign bodies from the surfaces thereof ina spot and film-free condition comprising treating said tableware with adilute aqueous solution of the composition defined in claim
 1. 15. Amethod of cleaning tableware by washing with an aqueous solution of thecomposition defined by claim
 8. 16. A method of safely cleaning finechina and other tableware by washing with an aqueous solution of thecomposition defined in claim 4.